Bond Coupled Electron Transfer Reactions

键耦合电子转移反应

• 批准号: 0111319
• 负责人: Joshua Goodman
• 金额: $ 32.7万
• 依托单位: University of Rochester
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-10-01 至 2006-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0111319&HistoricalAwards=false
• 关键词: Bond; Coupled; Electron; Transfer; Reactions

Professor Joshua Goodman of the Department of Chemistry at the University of Rochester, with the support of the Organic Dynamics Program, explores detailed mechanistic studies on different aspects of electron transfer reactions. The proposed research is centered on the concept that coupling the electron transfer processes to bond breaking and bond making events can increase the efficiency of electron transfer reactions. The research plan deals exclusively with the competition between return electron transfer (RET) and dissociative return electron transfer (DRET). The former is an energy-wasting decay process that has been widely studied in both singlet and triplet radical ion pairs. The latter is a rather specialized process that occurs only for triplet radical ion pairs under highly restrictive conditions for a limited set of substrates. Extensions of the scope of the DRET process will be of interest to specialists in the field of photoinduced electron transfer.Bond coupled electron transfer (BCET) reactions have the potential to drive chemical reactions. This project seeks to investigate several of these reactions. Professor Goodman will focus primarily on DRET reactions that involve cleavage of (1) C-C bonds in disubstituted cyclopropanes and diarylethanes, (2) Si-Si bonds in disilanes, and (3) C-halogen bonds in substituted benzylic halides. An improved understanding of RET processes in photoinduced electron transfer reactions may eventually lead to the ability to drive chemical reactions using light. For example, it may be possible one day to employ polymerizations induced by light in imaging applications. The proposed investigation on disilanes may have an impact on developing lithographic resists, nonlinear optical materials, and one-dimensional conductors.

罗彻斯特大学化学系的Joshua Goodman教授在有机动力学项目的支持下，对电子转移反应的不同方面进行了详细的机理研究。提出的研究集中在将电子转移过程与断键和成键事件耦合可以提高电子转移反应效率的概念上。本研究计划专门研究返回电子转移（RET）和解离返回电子转移（DRET）之间的竞争。前者是一种能量浪费衰变过程，在单线态和三重态自由基离子对中都得到了广泛的研究。后者是一个相当特殊的过程，只发生在高度限制条件下的三态自由基离子对对有限的底物。扩展DRET过程的范围将引起光致电子转移领域的专家的兴趣。键耦合电子转移（BCET）反应具有驱动化学反应的潜力。这个项目试图调查其中的几种反应。Goodman教授将主要关注涉及(1)二取代环丙烷和二乙烷中C-C键断裂的DRET反应，(2)二硅烷中的Si-Si键，以及(3)取代苯基卤化物中的c -卤素键断裂。对光诱导电子转移反应中RET过程的进一步了解可能最终导致利用光驱动化学反应的能力。例如，有一天可能在成像应用中使用光诱导的聚合。二硅烷的研究可能对光刻胶、非线性光学材料和一维导体的发展产生影响。